US2023240954A1PendingUtilityA1
Use of anthraquinone dyes and of fluorescent dyes for dyeing keratin fibres, dyeing process and composition
Est. expiryDec 22, 2036(~10.4 yrs left)· nominal 20-yr term from priority
A61K 8/355A61K 8/466A61Q 5/065A61K 8/4926A61K 2800/434A61K 8/49A61K 2800/432
44
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Claims
Abstract
Use of anthraquinone dyes and of fluorescent dyes for dyeing keratin fibres, dyeing process and composition. The present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, using a) one or more particular anthraquinone dyes and b) one or more fluorescent direct dyes; to a composition comprising a) and b). The present invention also relates to a multi-compartment device containing the compounds defined above.
Claims
exact text as granted — not AI-modified1 .- 27 . (canceled)
28 . A process for dyeing keratin fibers, comprising applying to the keratin fibers ingredients (a) and (b) below:
(a) at least one anthraquinone dye chosen from the compounds of formulae (I) and/or (II) below, optical isomers thereof, geometrical isomers thereof, tautomers thereof, solvates thereof, or mixtures thereof:
wherein in formula (I) or (II):
X a , which may be identical or different, represents a bond, a heteroatom or a group chosen from an oxygen or sulfur atom, N(R a ), CO, SO, SO 2 , or combinations thereof, with R a representing a hydrogen atom or a (C 1 -C 6 )alkyl group optionally substituted with one or more hydroxyl groups;
Y represents: i) a hydrogen atom; ii) an alkali metal; iii) an alkaline-earth metal; iv) an ammonium group: N + R a R b R g R d or a phosphonium group: P + R a R b R g R d with R a , R b , R g and R d , which may be identical or different, representing a hydrogen atom or a (C 1 -C 4 )alkyl group; or v) a thiol-function protecting group; or vi) the group (III) below:
R 1 , R 2 , R 3 , R 4 , R′ 1 , R′ 2 , R′ 3 and R′ 4 , which may be identical or different, represent an atom or a group chosen from:
hydrogen;
halogen such as bromine and chlorine,
hydroxyl,
C 1 -C 4 alkoxy,
hydroxysulfonyl (—SO 3 H) or sulfonate (—SO 3 − , M + ), with M + representing a cationic counterion;
optionally substituted C 1 -C 6 alkyl,
—NR 5 R 6 in which R 5 and R 6 , which may be identical or different, represent an atom or radical chosen from: i) hydrogen, ii) (C 1 -C 4 )alkylcarbonyl, iii) arylsulfonyl such as phenylsulfonyl (—SO 2 Ph), iv) Het-ALK-C(O)— with Het representing a heterocycloalkyl group which is optionally substituted and ALK represents a (C 1 -C 6 )alkylene group optionally substituted with one or more hydroxyl or (di)(hydroxy)(C 1 -C 4 )(alkyl)amino groups; v) optionally substituted aryl, vi) optionally substituted aryl(C 1 -C 4 )alkyl, viii) optionally substituted C 1 -C 20 alkyl, optionally interrupted with one or more heteroatoms and/or with one or more groups comprising at least one heteroatom;
a group of formula (a) below:
—N(R 7 )—X 1 —W 1 (a)
wherein in formula (a):
R 7 represents a hydrogen or a C 1 -C 4 alkyl radical,
X 1 represents a divalent radical chosen from C 1 -C 20 alkylene optionally interrupted with one or more heteroatoms or groups chosen from oxygen, nitrogen, sulfur, CO, SO, SO 2 , arylene, or combinations thereof;
W 1 represents a cationic radical chosen from:
with R 8 , R 9 , R 10 and R 11 , which may be identical or different, representing a C 1 -C 6 alkyl group, a benzyl radical, a C 1 -C 6 alkyl sulfonate radical; the radicals R 8 and R 9 optionally form, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising another non-nitrogen heteroatom;
n is an integer ranging from 1 to 3;
T 1 represents a linear or branched divalent hydrocarbon-based chain comprising from 1 to 20 carbon atoms, optionally interrupted with one or more heteroatoms or groups, or combinations thereof, chosen from oxygen, sulfur, N(R b ), C(O), —N + (R 8 )(R 9 )-An, optionally cationic and optionally substituted heteroaryl, An with R 8 and R 9 , which may be identical or different, represent a C 1 -C 6 alkyl radical; R b representing a hydrogen atom or a (hydroxy)(C 1 -C 4 )alkyl group;
being the part of the bond that is connected to the rest of the molecule; and
(b) at least one cationic (poly)methine fluorescent dye;
wherein:
the anthraquinone dye(s) of formula (I) comprise at least one radical R 1 , R 3 or R 4 , other than a hydrogen atom, and the anthraquinone dye(s) of formula (II) comprise at least one radical R′ 1 , R′ 2 , R′ 3 or R′ 4 other than a hydrogen atom;
(a) the anthraquinone dye(s) of formula (I) or (II) and (b) the fluorescent dye(s) are applied to said keratin fibers together or sequentially; and
when the compounds of formula (I) or (II) are cationic and comprise a sulfonate group, then M + and An are optionally absent to ensure the electrical neutrality of said molecule.
29 . The process according to claim 28 , wherein the at least one anthraquinone dye of formulae (I) and/or (II) absorbs light in the blue-violet range.
30 . The process according to claim 28 , wherein the at least one anthraquinone is chosen from compounds of formula (I) wherein n is equal to 0 or 1.
31 . The process according to claim 28 , wherein the at least one anthraquinone dye is chosen from compounds of formula (I), wherein R 1 and R 3 represent an atom or group chosen from i) hydroxyl, ii) arylamino or aryl(C 1 -C 6 )alkylamino with the aryl group representing an optionally substituted aryl group, iii) (di)(hydroxy)(C 1 -C 6 )(alkyl)amino, iv) (di)(C 1 -C 4 )(alkyl)amino(C 1 -C 6 )alkylamino, v) (C 1 -C 4 )alkylcarbonylamino(C 1 -C 6 )alkylamino, vi) arylsulfonylamino with the aryl group optionally substituted, vii) (di)halo(C 1 -C 4 )alkylamino, viii) (di)(hydroxy)(C 1 -C 4 )alkoxy(C 1 -C 4 )alkylamino, ix) (di)tri(C 1 -C 4 )alkylammonium(C 1 -C 6 )alkylamino, x) heterocycloalkyl(C 1 -C 6 )alkylamino, heterocycloalkyl(C 1 -C 4 )alkylcarbonylamino, heterocycloalkyl(C 1 -C 4 )alkylamino(C 1 -C 4 )alkylcarbonylamino or heterocycloalkyl(C 1 -C 4 )alkylcarbonylamino(C 1 -C 6 )alkylamino, wherein the heterocycloalkyl is optionally cationic, xi) halo(C 1 -C 4 )alkylcarbonylamino(C 1 -C 6 )alkylamino, xii) hydroxysulfonyl, xiii) halo, xiv) heteroaryl(C 1 -C 6 )alkylamino, wherein the heteroaryl is optionally cationic and/or substituted, xv) heteroaryl(C 1 -C 4 )alkylcarbonylamino(C 1 -C 6 )alkylamino, wherein the heteroaryl is optionally cationic and/or substituted, xvi) R′R″N— with R′ and R″, which may be identical or different, representing a (halo)(C 1 -C 4 )alkylcarbonylamino(C 1 -C 6 )alkyl group, a (halo)(C 1 -C 4 )alkylaminocarbonyl (C 1 -C 6 )alkyl group, a (halo)(C 1 -C 4 )alkylcarbonyl group, a carboxy(C 1 -C 6 )alkyl group, the alkyl group possibly being substituted with one or more amino or hydroxyl groups, a (poly)hydroxy(C 1 -C 6 )alkyl group, xvii) (C 1 -C 16 )alkylaminocarbonylamino(C 1 -C 6 )alkylamino, xviii) formylamino(C 1 -C 6 )alkylamino, xix) (hydroxy)(C 1 -C 6 )alkylamino(C 1 -C 6 )alkylamino, xix) hydroxysulfonyl(C 1 -C 6 )alkylamino(C 1 -C 6 )alkylamino, xx) sulfonato(C 1 -C 6 )alkyl(di(C 1 -C 4 )alkyl)ammonium(C 1 -C 6 )alkylamino, xxi) hydroxysulfonyl(C 1 -C 6 )alkoxy(C 1 -C 6 )alkylamino, xxi) heteroaryl(C 1 -C 4 )alkylcarbonylamino, wherein the heteroaryl is optionally cationic and/or substituted, xxii) heterocycloalkyl(C 1 -C 4 )alkylcarbonylamino, wherein the heterocycloalkyl is optionally cationic and/or substituted, xxiii) (di)(C 1 -C 4 )(alkyl)amino(C 1 -C 6 )alkylamino, wherein the (C 1 -C 6 )alkyl group is optionally substituted with one or more hydroxyl groups, xxiv) heterocycloalkylamino(C 1 -C 6 )alkylamino or heterocycloalkylamino, wherein the heterocycloalkyl is optionally cationic and/or substituted, xxv) heteroarylalkylamino(C 1 -C 6 )alkylamino or heteroarylalkylamino, wherein the heteroaryl is optionally cationic and/or substituted, xxvi) tri(C 1 -C 6 )alkylammonium(C 1 -C 6 )alkylamino, xxvii) (C 1 -C 4 )alkoxycarbonyl(C 1 -C 6 )alkyl(di(C 1 -C 4 )alkyl)ammonium(C 1 -C 6 )alkylamino, xxviii) carboxylato(C 1 -C 6 )alkyl(di(C 1 -C 4 )alkyl)ammonium(C 1 -C 6 )alkylamino, xxix) carboxy(C 1 -C 6 )alkylamino(C 1 -C 6 )alkylamino, xxx) aryl(C 1 -C 4 )alkyl(di(C 1 -C 4 )alkyl)ammonium(C 1 -C 6 )alkylamino, xxxi) sulfonic SO 3 H or sulfonate SO 3 − , M + with M + representing a cationic counterion, xxxii) (C 1 -C 6 )alkyl, xxxiii) hydroxysulfonyl(C 1 -C 4 )amino, xxxiv) phenylsulfonylamino.
32 . The process according to claim 28 , wherein the at least one anthraquinone dye is chosen from dyes of formula (I), wherein R 2 and R 4 , which may be identical or different, represent a hydrogen atom or a group chosen from:
hydroxyl, (di)(C 1 -C 4 )(alkyl)amino, (C 1 -C 4 )alkoxy, heterocycloalkyl(C 1 -C 6 )alkylamino, wherein the heterocycloalkyl is optionally cationic and/or substituted, arylamino or aryl(C 1 -C 6 )alkylamino wherein the aryl group is an optionally substituted aryl group, aryl(C 1 -C 4 )alkyl(di(C 1 -C 4 )alkyl)ammonium(C 1 -C 6 )alkylamino, (di)(C 1 -C 4 )(alkyl)amino(C 1 -C 6 )alkylamino, or hydroxy(C 1 -C 4 )(alkyl)amino(C 1 -C 6 )alkylamino.
33 . The process according to claim 28 , wherein the at least one anthraquinone dye is chosen from dyes of formula (I), and R 2 and R 4 represent a hydrogen atom.
34 . The process according to claim 28 , wherein the at least one anthraquinone dye of formulae (I) and/or (II) is chosen from dyes of formula (I) with R 2 and R 3 representing a hydrogen atom, and R 1 and R 4 are chosen from:
halogen, (di)(C 1 -C 4 )(alkyl)amino, (C 1 -C 4 )alkylcarbonylamino, heterocycloalkyl(C 1 -C 6 )alkylamino, heterocycloalkyl(C 1 -C 4 )alkylcarbonylamino or heterocycloalkyl(C 1 -C 4 )alkylamino(C 1 -C 4 )alkylcarbonylamino, wherein the heterocycloalkyl is optionally cationic and/or substituted, tri(C 1 -C 4 )alkylammonium(C 1 -C 6 )alkylamino, arylamino or aryl(C 1 -C 6 )alkylamino wherein the aryl group si an optionally substituted aryl group, (di)(C 1 -C 4 )(alkyl)amino(C 1 -C 6 )alkylamino, or (C 1 -C 4 )alkylcarbonylamino(C 1 -C 6 )alkylamino.
35 . The process according to claim 28 wherein the anthraquinone dye(s) of formulae (I) and/or (II) are dyes of formula (I) with R 3 and R 4 representing a hydrogen atom, and R 1 and R 2 are in positions 8 and 1, respectively, and R 1 and R 2 are chosen from:
(di)(hydroxy)(C 1 -C 4 )(alkyl)amino,
(di)(hydroxy)(C 1 -C 4 )(alkyl)amino(C 1 -C 6 )alkylamino,
tri(C 1 -C 6 )alkylammonium(C 1 -C 6 )alkylammonium,
tri(C 1 -C 6 )alkylammonium(C 1 -C 6 )alkylamino,
heterocycloalkyl(C 1 -C 6 )alkylamino, said heterocycloalkyl possibly being optionally cationic and/or substituted especially with one or more (C 1 -C 4 ) alkyl or benzyl groups and
arylamino or aryl(C 1 -C 6 )alkylamino with the aryl group representing an optionally substituted aryl group, in particular a phenyl group optionally substituted with one or more groups chosen from (C 1 -C 4 )alkyl, (di)(hydroxy)(C 1 -C 4 )(alkyl)amino, (C 1 -C 4 )alkoxy, tri(C 1 -C 4 )alkylammonium.
36 . The process according to claim 28 , wherein the at least one anthraquinone dye is chosen from dyes of formula (I) with R 1 and R 3 representing a hydrogen atom and n is equal to 2, and R 2 and R 4 are chosen from:
(C 1 -C 6 )alkyl, (di)(hydroxy)(C 1 -C 4 )(alkyl)amino, SO 3 H or SO 3 − M + , (di)(hydroxy)(C 1 -C 4 )(alkyl)amino(C 1 -C 6 )alkylamino, tri(C 1 -C 4 )alkylammonium(C 1 -C 6 )alkylamino, and heterocycloalkyl(C 1 -C 6 )alkylamino, wherein the heterocycloalkyl si optionally cationic and/or substituted, or arylamino or aryl(C 1 -C 6 )alkylamino with the aryl group representing an optionally substituted aryl group.
37 . The process according to claim 28 , wherein the at least one anthraquinone dye is chosen from dyes of formula (II′):
wherein X a represents an N(R a ), R′ 2 and R′ 4 represent a hydrogen atom and; T 1 represents a saturated linear divalent hydrocarbon-based chain comprising from 1 to 20 carbon atoms, optionally interrupted with one or more groups chosen from N(R b ), C(O), —N + (R 8 )(R 9 )-An, cationic heteroaryl, An, or combinations thereof, with R 8 and R 9 , which may be identical or different, representing a C 1 -C 6 alkyl radical; R b representing a hydrogen atom or a (C 1 -C 4 )alkyl group.
38 . The process according to claim 37 , wherein the at least one anthraquinone dye is chosen from the dyes of formula (II″):
39 . The process according to claim 28 , wherein the at least one anthraquinone dye of formulae (I) and/or (II) is chosen from the following compounds, optical isomers thereof, geometrical isomers thereof, tautomers thereof, solvates thereof, or mixtures thereof:
wherein An, which may be identical or different, represents an anionic counterion chosen from mesylate, tosylate, or halide.
40 . The process according to claim 28 , wherein the at least one cationic (poly)methine fluorescent dye is chosen from direct dyes chosen from cyanin dyes, styryl/hemicyanin dyes, naphthalimide dyes, or mixtures thereof.
41 . The process according to claim 28 , wherein the at least one cationic (poly)methine fluorescent dye is chosen from dyes which absorb light in the yellow, orange and red range.
42 . The process according to claim 28 , wherein the at least one cationic (poly)methine fluorescent dye is chosen from dyes which bear at least one cationic chromophore chosen from formulae (III), (IV), (IIIa), or (IVa) below:
W + —[C(R c )═C(R d )] m′ —Ar′-(*)Q − (I)
Ar—[C(R d )═C(R c )] m′ —W′ + -(*)Q − (IV),
wherein in formulae (III) and (IV):
W + represents a cationic heteroaryl group comprising a quaternary ammonium optionally substituted with one or more (C 1 -C 8 )alkyl groups optionally substituted with one or more hydroxyl groups;
W′ + represents a divalent heteroaryl radical as defined for W + ;
Ar represents an aryl group, optionally substituted with i) one or more halogen atoms such as chlorine or fluorine; ii) one or more (C 1 -C 8 )alkyl; iii) one or more hydroxyl groups; iv) one or more (C 1 -C 8 )alkoxy groups; v) one or more hydroxy(C 1 -C 8 )alkyl groups, vi) one or more amino or (di)(C 1 -C 8 )alkylamino groups, vii) with one or more acylamino groups; viii) one or more heterocycloalkyl groups;
Ar′ is a divalent aryl radical;
m′ represents an integer between 1 and 4 inclusive;
R c and R d , which may be identical or different, represent a hydrogen atom or optionally a substituted (C 1 -C 8 )alkyl, or alternatively R c is contiguous with W or W′ and/or R d is contiguous with Ar or Ar′ and form, with the atoms that bear them, a (hetero)cycloalkyl;
Q − is an organic or mineral anionic counterion;
(*) represents the part of the fluorescent chromophore that is bonded to the rest of the dye,
wherein in formulae (IIIa) and (IVa) R e , R f , R g and R h , which may be identical or different, represent a hydrogen atom or a (C 1 -C 6 )alkyl group which is optionally substituted.
43 . The process according to claim 28 , wherein the at least one cationic (poly)methine fluorescent dye is chosen from the dyes of formulae (V), (VI), or (VII):
organic or mineral acid or base salts thereof, optical isomers, geometrical isomers thereof, tautomers thereof, or solvates thereof;
wherein:
R 1 and R 2 , which may be identical or different, represent a hydrogen atom or a C 1 -C 6 alkyl group;
G 1 represents a hydrogen atom or a group chosen from NH 2 and OH;
R a , R′ a , R″ a , R′″ a , R b , R′ b , R″ b , and R′″ b , which may be identical or different, represent a) a hydrogen atom, b) a halogen atom, a group chosen from: c) amino, d) (C 1 -C 4 )alkylamino, e) (C 1 -C 4 )dialkylamino, f) cyano, g) carboxyl —C(O)OH or carboxylate —C(O)O − , Q + , h) hydroxy —OH or alkoxide —O − Q + , i) (poly)halo(C 1 -C 6 )alkyl j) acylamino, k) (C 1 -C 6 )alkoxy, l) (C 1 -C 6 )alkylthio, m) (poly)hydroxy(C 2 -C 4 )alkoxy, n) (C 1 -C 6 )alkylcarbonyloxy, o) (C 1 -C 6 )alkoxycarbonyl, p) (C 1 -C 6 )alkylcarbonylamino, q) acylamino, r) carbamoyl, s) (C 1 -C 6 )alkylsulfonylamino, t) aminosulfonyl, u) —SO 3 H or sulfonate —SO 3 − , Q + or v) (C 1 -C 6 )alkyl optionally substituted with a group chosen from (C 1 -C 6 )alkoxy, hydroxyl, cyano, carboxyl, amino, (di)(C 1 -C 4 )alkylamino, or alternatively the two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom;
or alternatively two groups R a and R′ a ; R b and R′ b , borne by two adjacent carbon atoms, together form a benzo or indeno ring, a fused heterocycloalkyl or fused heteroaryl group; the benzo, indeno, heterocycloalkyl or heteroaryl ring being optionally substituted with a halogen atom, an amino, (C 1 -C 4 )alkylamino, (C 1 -C 4 )dialkylamino, nitro, cyano, carboxyl, hydroxyl or trifluoromethyl group, an acylamino, (C 1 -C 4 )alkoxy (poly)hydroxy(C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylcarbonyloxy, (C 1 -C 4 )alkoxycarbonyl or (C 1 -C 4 )alkylcarbonylamino radical, an acylamino, carbamoyl or alkoxyalkylsulfonylamino radical, an aminosulfonyl radical, or a (C 1 -C 6 )alkyl radical optionally substituted with: a group chosen from (C 1 -C 6 )alkoxy, hydroxyl, cyano, carboxyl, amino, (C 1 -C 4 )alkylamino, or (C 1 -C 4 )dialkylamino, or alternatively the two alkyl radicals borne by the nitrogen atom of the amino group form a 5- to 7-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom;
or alternatively, two groups R i and R a ; and/or a group R′ i and R′ a together form a fused (hetero)cycloalkyl;
R g represents a hydrogen atom, a (hetero)aryl(C 1 -C 4 )alkyl group or a (C 1 -C 6 )alkyl group that is optionally substituted;
R e represents a covalent bond, a linear or branched, optionally substituted (C 1 -C 8 )alkylene or (C 2 -C 8 )alkenylene hydrocarbon-based chain
R f represents a hydrogen atom, a (C 1 -C 4 )alkoxy group, an amino group R 3 R 4 N—, a quaternary ammonium group M′, R 3 R 4 R 5 N + — in which R 3 , R 4 and R 5 , which may be identical or different, represent a hydrogen atom or a (C 1 -C 4 )alkyl group or R 3 R 4 N— represents an optionally substituted heteroaryl group, or alternatively M′, R 3 R 4 R 5 N + — represents an optionally substituted cationic heteroaryl group;
G represents a group i) —NR c R d , ii) —OR with R representing a) a hydrogen atom, b) an optionally substituted, preferentially unsubstituted (C 1 -C 6 )alkyl group, c) an optionally substituted (hetero)aryl group, d) an optionally substituted (hetero)aryl(C 1 -C 6 )alkyl group such as benzyl, e) optionally substituted (hetero)cycloalkyl group, f) optionally substituted (hetero)cycloalkyl(C 1 -C 6 )alkyl group;
or alternatively when G represents —NR c R d , two groups R c and R′ a and/or R d and R a together form a saturated heteroaryl or heterocycle, optionally substituted with one or more (C 1 -C 6 )alkyl groups;
R c and R d , which may be identical or different, represent a hydrogen atom or a group chosen from: a) optionally substituted (hetero)aryl, b) optionally substituted (hetero)aryl(C 1 -C 4 )alkyl, c) optionally substituted (hetero)cycloalkyl, d) optionally substituted (hetero)cycloalkyl(C 1 -C 4 )alkyl, f) (C 2 -C 5 )alkyl, or g) (C 1 -C 8 )alkyl which is optionally substituted;
or alternatively two adjacent radicals R c and R d borne by the same nitrogen atom together form an optionally substituted heterocyclic or optionally substituted heteroaryl group;
R i and R′ i , which may be identical or different, represent a hydrogen atom or a (C 1 -C 4 )alkyl group;
represents a (hetero)aryl group fused to the phenyl ring; or alternatively is absent from the phenyl;
m represents an integer between 1 and 18 inclusive;
M′ represents an anionic counterion, derived from a salt of an organic or mineral acid, or from an organic or mineral base that ensures the electrical neutrality of the molecule;
Q + represents a cationic counterion, derived from a salt of an organic or mineral acid, or from an organic or mineral base that ensures the electrical neutrality of the molecule such as alkali metal, alkaline-earth metal or ammonium;
wherein when the molecule comprises a carboxylate, sulfonate or alkoxide group, then M′ and Q + may be absent to ensure the electrical neutrality of said molecule.
44 . The process according to claim 28 , wherein the at least one cationic (poly)methine fluorescent dye is chosen from styryl dyes of formula (VIII) below:
organic or mineral acid or base salts thereof, optical isomers thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof;
wherein
R 1 and R 2 , which may be identical or different, represent a hydrogen atom;
R i and R i′ , which may be identical or different, represent a hydrogen atom or a (C 1 -C 4 )alkyl group;
R a , R′ a and R″ a , which may be identical or different, represent a hydrogen atom, a halogen atom, or an —OH, —O − Q + , (C 1 -C 6 )alkoxy, nitro, or cyano group, wherein Q + represents a cationic counterion, derived from a salt of an organic or mineral acid, or from an organic or mineral base that ensures the electrical neutrality of the molecule;
R b , R′ b and R″ b , which may be identical or different, represent a hydrogen atom or a (C 1 -C 6 )alkyl group;
or alternatively two contiguous radicals R b and R′ b form, together with the carbon atoms that bear them, a benzo group that is condensed or fused to the pyridinium group, said benzo group optionally substituted;
G represents a group —NR c R d or (C 1 -C 6 )alkoxy group which is optionally substituted;
G 1 represents a hydrogen atom or an OH or NH 2 group;
R i and R′ i , which may be identical or different, represent a hydrogen atom or a (C 1 -C 4 )alkyl group;
represents an aryl or heteroaryl group fused to the phenyl ring; or alternatively is absent from the phenyl ring;
m represents an integer between 1 and 18 inclusive;
R c and R d , which may be identical or different, represent a hydrogen atom, a (C 2 -C 4 )alkyl group or a substituted (C 1 -C 8 )alkyl group; and
M′ represents an anionic counterion, derived from a salt of an organic or mineral acid, or from an organic or mineral base that ensures the electrical neutrality of the molecule;
wherein when the molecule comprises an alkoxide group, then M′ and Q + are optionally absent to ensure the electrical neutrality of said molecule.
45 . The process according to claim 28 , wherein the at least one cationic (poly)methine fluorescent dye is chosen from the dyes of the compounds of formulae (X), (XI), (XII), or (XIII) below:
organic or mineral acid salts thereof, optical isomers thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof;
wherein in formula (X), (XI), (XIII), or (XIII):
R 1 , R 2 , R 3 and R 4 , which may be identical or different, represent a hydrogen atom or a (C 1 -C 6 )alkyl group;
R 5 , R 6 , R 7 , R 8 and R 9 , which may be identical or different, represent i) a hydrogen atom or ii) a halogen atom, iii) a group OR in which R represents a hydrogen atom or Q + represents a cationic counterion, derived from a salt of an organic or mineral acid, or from an organic or mineral base that ensures the electrical neutrality of the molecule, or a (C 1 -C 3 )alkyl group, iv) aryl, v) an aryl(C 1 -C 3 )alkyl group, vi) cyano, vii) nitro, viii) (C 1 -C 3 )alkylthio, ix) amino NR 10 R 11 with R 10 and R 11 , which may be identical or different, representing a) a hydrogen atom, b) a (C 2 -C 4 )alkyl group or c) a substituted (C 1 -C 8 )alkyl group:
cyano,
(C 1 -C 3 )alkoxy,
hydroxyl, and
(C 1 -C 3 )alkylcarbonyl;
m represents an integer between 1 and 18 inclusive;
M′ represents an anionic counterion, derived from a salt of an organic or mineral acid, or from an organic or mineral base that ensures the electrical neutrality of the molecule;
wherein when the molecule comprises an alkoxide group, then M′ and Q + are optionally absent to ensure the electrical neutrality of the molecule.
46 . The process according to claim 28 , wherein the at least one cationic (poly)methine fluorescent dye is chosen from those of formulae (XIV) or (XV) below:
wherein:
R 5 and R 8 , which may be identical or different, represent a hydrogen atom or a (C 1 -C 4 )alkoxy group;
R 7 represents a (C 1 -C 4 )alkoxy group or NR 10 R 11 with R 10 and R 11 , which may be identical or different, representing a) a hydrogen atom, or b) a (C 1 -C 8 )alkyl group optionally substituted with one or more groups chosen from i) hydroxyl, ii) R—Z—C(X)—Y— with X, Y and Z representing an oxygen or sulfur atom or N(R′), or alternatively X and/or Z represent a bond, R and R′, which may be identical or different, represent a hydrogen atom or a (C 1 -C 6 )alkyl group, iii) sulfonic SO 3 H, iv) sulfonate SO 3 − , Q + , v) carboxylate C(O)O − , Q + with Q + representing a cationic counterion;
m represents an integer between 1 and 18 inclusive; and
M′ represents an anionic counterion, derived from a salt of an organic or mineral acid, or from an organic or mineral base that ensures the electrical neutrality of the molecule;
wherein when the molecule comprises an alkoxide group, then M′ and Q + are optionally absent to ensure the electrical neutrality of said molecule.
47 . The process according to claim 46 , wherein:
the at least one cationic (poly)methine fluorescent dye is chosen from compounds of formula (X), wherein:
R 1
R 2
R 3
R 4
R 5
R 6
R 7
R 8
R 9
m
H
H
H
H
H
H
H
H
H
1
H
H
H
H
H
t-Bu
OH
t-Bu
H
5
H
H
H
H
H
t-Bu
OH
t-Bu
H
5
H
H
H
H
H
H
NH 2
H
H
1
H
H
H
H
H
H
NH 2
H
OCH 3
1
H
H
H
H
H
H
OH
Br
H
5
H
H
H
H
H
OCH 3
OH
OCH 3
H
5
H
H
H
H
Cl
H
OH
H
Cl
5
H
H
H
H
H
H
OH
H
H
10
H
H
H
H
H
OCH 3
OH
OCH 3
H
10
H
H
H
H
H
t-Bu
OH
t-Bu
H
10
H
H
H
H
H
H
N(CH 2 CH 3 ) 2
H
H
1
H
H
H
H
H
H
N(CH 2 CH 3 ) 2
H
H
1
H
H
H
H
H
H
N(CH 2 CH 3 ) 2
H
H
1
H
H
H
H
H
t-Bu
OH
t-Bu
H
10
H
H
H
H
H
H
N(CH 2 CH 3 )CH 2 CH 2 OH
H
H
1
H
H
H
H
H
H
N(CH 2 CH 3 ) 2
H
H
1
H
H
H
H
H
H
N(CH 2 CH 3 ) 2
H
H
1
H
H
H
H
H
H
N(CH 2 CH 3 ) 2
H
H
1
H
H
H
H
H
H
N(CH 2 CH 3 ) 2
H
H
1
H
H
H
H
H
H
N(CH 2 CH 3 ) 2
H
H
1
H
H
H
H
H
H
N(CH 2 CH 3 ) 2
H
H
1
H
H
H
H
H
H
N(CH 2 CH 3 ) 2
H
H
1
H
H
H
H
H
H
N(CH 2 CH 3 ) 2
H
H
1
H
H
H
H
H
H
N(CH 2 CH 3 ) 2
H
H
1
H
H
H
H
H
H
n-C 6 H 13
H
H
1
H
H
H
H
H
H
N(CH 2 CH 2 OH) 2
H
H
2
H
H
H
H
H
H
N(n-Bu) 2
H
H
2
H
H
H
H
H
OCH 3
OH
H
H
10
H
H
H
H
H
H
OC 2 H 5 OH
H
H
1
H
H
H
H
H
H
OH
H
H
1
H
H
benzo
H
H
H
H
H
1
H
H
benzo
H
H
N(CH 2 CH 2 OH) 2
H
H
1
H
H
benzo
H
H
N(CH 2 CH 2 OH) 2
H
H
1
organic or mineral acid or base salts thereof, optical isomers, geometrical isomers thereof, tautomers thereof, or solvates thereof;
cationic (poly)methine fluorescent dyes of formula (XI), wherein:
R 1
R 2
R 3
R 4
R 5
R 6
R 7
R 8
R 9
m
CH 3
H
H
H
OH
H
OCH 3
H
H
2
CH 3
H
H
H
H
H
OCH 3
OCH 2 —Ph
H
2
CH 3
H
H
H
H
H
H
H
OCH 3
2
CH 3
H
H
H
F
H
H
H
H
2
CH 3
H
H
H
H
H
H
OPh
H
2
CH 3
H
H
H
H
H
N(CH 2 CH 2 OAc) 2
H
H
2
CH 3
H
H
H
OCH 3
H
OCH 3
OCH 3
H
2
CH 3
H
H
H
H
H
H
CH 3
H
2
CH 3
H
H
H
H
H
OH
H
H
2
CH 3
H
H
H
H
OCH 3
OCH 3
OCH 3
H
2
CH 3
H
H
H
H
OCH 3
OH
OH
H
2
CH 3
H
H
H
H
H
OCH 3
OCH 3
OCH 3
2
CH 3
H
H
H
H
H
H
OCH 3
OH
2
CH 3
H
H
H
H
H
N(n-butyl) 2
H
H
2
CH 3
H
H
H
H
OCH 3
OCH 3
H
H
2
CH 3
H
H
H
H
H
H
H
H
2
CH 3
H
H
H
H
H
i-propyl
H
H
2
H
H
H
H
H
H
OH
H
H
6
H
H
H
H
H
OCH 3
OCH 3
OCH 3
H
6
H
H
H
H
OH
H
OCH 3
H
H
2
H
H
H
H
OCH 3
H
H
OCH 3
OCH 3
2
H
H
H
H
H
H
H
H
Br
2
H
H
H
H
H
H
OH
H
H
2
H
H
H
H
OCH 3
OCH 3
OCH 3
H
H
6
H
H
H
H
OH
OCH 3
H
H
H
6
H
H
H
H
H
OCH 3
OCH 3
H
H
6
H
H
H
H
H
OCH 3
OCH 3
H
H
2
H
H
H
H
H
H
C(O)—OH
H
H
6
H
H
H
H
H
H
C(O)—OH
H
H
2
H
H
H
H
H
H
i-propyl
H
H
2
H
H
H
H
H
H
N(CH 3 )CH 2 CH 2 CN
H
H
2
H
H
H
H
H
H
OCH 3
OCH 2 Ph
H
2
H
H
H
H
H
H
H
OPh
H
2
H
H
H
H
H
H
N(CH 2 CH 2 C(O)CH 3 ) 2
H
H
2
H
H
H
H
OH
H
OCH 3
H
H
6
H
H
H
H
H
OCH 3
OCH 3
OCH 3
H
2
H
H
H
H
OCH 3
H
OCH 3
OCH 3
H
6
H
H
H
H
H
H
H
CH 3
H
2
H
H
H
H
H
H
N(CH 3 )CH 2 CH 2 OH
H
H
2
organic or mineral acid or base salts thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof;
cationic (poly)methine fluorescent dyes of formulae (X′) or (XI′):
wherein
R 5
R 7
R 8
m
R 5
R 7
R 8
M
H
N(CH 2 CH 2 OH) 2
H
2
and
OCH 3
OCH 3
OCH 3
2
H
N(CH 2 CH 2 OH) 2
H
3
OCH 3
OCH 3
OCH 3
3
H
N(CH 2 CH 2 OH) 2
H
4
OCH 3
OCH 3
OCH 3
3
H
N(CH 2 CH 2 OH) 2
H
5
OCH 3
OCH 3
OCH 3
4
H
N(CH 2 CH 2 OH) 2
H
6
OCH 3
OCH 3
OCH 3
5
H
N(CH 2 CH 2 OH) 2
H
8
OCH 3
OCH 3
OCH 3
8
H
N(CH 2 CH 2 OH) 2
H
10
OCH 3
OCH 3
OCH 3
10
H
N(CH 2 CH 2 OH) 2
H
12
OCH 3
OCH 3
OCH 3
12
H
N(CH 2 CH 2 OH) 2
H
14
OCH 3
OCH 3
OCH 3
14
H
N(CH 2 CH 2 OH) 2
H
16
OCH 3
OCH 3
OCH 3
16
H
CH 3 CH 2 N(CH 2 CH 2 OH)
H
2
H
CH 3 CH 2 N(CH 2 CH 2 OH)
H
4
organic or mineral acid or base salts thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof;
cationic (poly)methine fluorescent dyes of formula (XII) wherein:
R 1
R 2
R 3
R 4
R 5
R 6
R 7
R 8
R 9
m
H
H
H
H
H
H
OCH 3
OCH 3
OCH 3
2
H
H
H
H
OH
OCH 3
H
H
H
2
H
H
H
H
H
H
H
H
H
2
H
H
H
H
H
OCH 3
OCH 3
H
H
2
H
H
H
H
OH
H
OH
H
H
6
H
H
H
H
OCH 3
H
OCH 3
OCH 3
H
6
H
H
H
H
H
H
OH
H
H
6
H
H
H
H
OCH 3
H
H
H
F
2
H
H
H
H
H
H
C(O)—OH
H
H
2
H
H
H
H
H
H
Isopropyl
H
H
2
H
H
H
H
H
H
N(CH 2 CH 2 C(O)CH 3 ) 2
H
H
2
H
H
H
H
OH
H
OCH 3
H
H
2
H
H
H
H
H
H
OH
H
H
2
H
H
H
H
H
OCH 3
OH
OH
H
2
H
H
H
H
H
CH 3
OCH 2 Ph
CH 3
H
2
H
H
H
H
H
OCH 3
OCH 3
OCH 3
H
2
H
H
H
H
H
OCH 3
OCH 3
OCH 3
H
6
H
H
H
H
H
H
N(CH 3 ) 2
H
H
6
H
H
H
H
H
H
OCH 3
OCH 3
OCH 3
6
H
H
H
H
H
H
Phenyl
H
H
6
H
H
H
H
H
OCH 3
OCH 3
H
H
6
H
H
H
H
H
H
C(O)—OH
H
H
6
H
H
H
H
H
H
N(n-Butyl) 2
H
H
2
H
H
H
H
H
H
OCH 3
OCH 3
H
3
H
H
H
H
H
H
OCH 3
OCH 3
H
2
H
H
H
H
H
H
OCH 3
OCH 3
H
5
H
H
H
H
H
H
OCH 3
H
H
3
H
H
H
H
H
H
N(CH 3 ) 2
H
H
3
H
H
H
H
H
H
H
H
H
3
organic or mineral acid or base salts thereof, optical isomers thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof;
cationic (poly)methine fluorescent dyes of formula (XIII), wherein:
R 1
R 2
R 3
R 4
R 5
R 6
R 7
R 8
R 9
m
CH 3
H
H
H
OH
H
OCH 3
H
H
2
CH 3
H
H
H
H
H
OCH 3
OCH 2 —Ph
H
2
CH 3
H
H
H
H
H
H
H
OCH 3
2
CH 3
H
H
H
F
H
H
H
H
2
CH 3
H
H
H
H
H
H
OPh
H
2
CH 3
H
H
H
H
H
N(CH 2 CH 2 OAc) 2
H
H
2
CH 3
H
H
H
OCH 3
H
OCH 3
OCH 3
H
2
CH 3
H
H
H
H
H
H
CH 3
H
2
CH 3
H
H
H
H
H
OH
H
H
2
CH 3
H
H
H
H
OCH 3
OCH 3
OCH 3
H
2
CH 3
H
H
H
H
OCH 3
OH
OH
H
2
CH 3
H
H
H
H
H
OCH 3
OCH 3
OCH 3
2
CH 3
H
H
H
H
H
H
OCH 3
OH
2
CH 3
H
H
H
H
H
N(n-butyl) 2
H
H
2
CH 3
H
H
H
H
OCH 3
OCH 3
H
H
2
CH 3
H
H
H
H
H
H
H
H
2
CH 3
H
H
H
H
H
i-propyl
H
H
2
H
H
H
H
H
H
OH
H
H
6
H
H
H
H
H
OCH 3
OCH 3
OCH 3
H
6
H
H
H
H
OH
H
OCH 3
H
H
2
H
H
H
H
OCH 3
H
H
OCH 3
OCH 3
2
H
H
H
H
H
H
H
H
Br
2
H
H
H
H
H
H
OH
H
H
2
H
H
H
H
H
H
N(CH 3 ) 2
H
H
6
H
H
H
H
OCH 3
OCH 3
OCH 3
H
H
6
H
H
H
H
OH
OCH 3
H
H
H
6
H
H
H
H
H
OCH 3
OCH 3
H
H
6
H
H
H
H
H
OCH 3
OCH 3
H
H
2
H
H
H
H
H
H
C(O)—OH
H
H
6
H
H
H
H
H
H
C(O)—OH
H
H
2
H
H
H
H
H
H
i-propyl
H
H
2
H
H
H
H
H
H
N(CH 3 )CH 2 CH 2 CN
H
H
2
H
H
H
H
H
H
OCH 3
OCH 2 Ph
H
2
H
H
H
H
H
H
H
OPh
H
2
H
H
H
H
H
H
N(CH 2 CH 2 C(O)CH 3 ) 2
H
H
2
H
H
H
H
OH
H
OCH 3
H
H
6
H
H
H
H
H
OCH 3
OCH 3
OCH 3
H
2
H
H
H
H
OCH 3
H
OCH 3
OCH 3
H
6
H
H
H
H
H
H
H
CH 3
H
2
H
H
H
H
H
H
N(CH 3 )CH 2 CH 2 OH
H
H
2
CH 3
H
H
H
H
H
N(CH 3 ) 2
H
H
2
organic or mineral acid or base salts thereof, geometrical isomers thereof, tautomers thereof, or the solvates thereof;
cationic (poly)methine fluorescent dyes of formulae (XII′) or (XIII′) below:
wherein:
R 5
R 7
R 8
m
R 5
R 7
R 8
m
H
N(CH 2 CH 2 OH) 2
H
2
and
OCH 3
OCH 3
OCH 3
2
H
N(CH 2 CH 2 OH) 2
H
3
OCH 3
OCH 3
OCH 3
3
H
N(CH 2 CH 2 OH) 2
H
4
OCH 3
OCH 3
OCH 3
3
H
N(CH 2 CH 2 OH) 2
H
5
OCH 3
OCH 3
OCH 3
4
H
N(CH 2 CH 2 OH) 2
H
6
OCH 3
OCH 3
OCH 3
5
H
N(CH 2 CH 2 OH) 2
H
8
OCH 3
OCH 3
OCH 3
8
H
N(CH 2 CH 2 OH) 2
H
10
OCH 3
OCH 3
OCH 3
10
H
N(CH 2 CH 2 OH) 2
H
12
OCH 3
OCH 3
OCH 3
12
H
N(CH 2 CH 2 OH) 2
H
14
OCH 3
OCH 3
OCH 3
14
H
N(CH 2 CH 2 OH) 2
H
16
OCH 3
OCH 3
OCH 3
16
organic or mineral acid or base salts thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof;
cationic (poly)methine fluorescent dyes chosen from the following compounds:
organic or mineral acid or base salts thereof, geometrical isomers thereof, tautomers thereof, or the solvates thereof.
48 . The process according to claim 28 , wherein the process further comprises applying to said keratin fibers a cosmetic composition comprising c) one or more reducing agents.
49 . The process according to claim 28 , wherein the process does not use any reducing agent.
50 . The process according to claim 28 , wherein the at least one anthraquinone compound and the at least one cationic (poly)methine fluorescent direct dye are applied together to the keratin fibers.
51 . The process according to claim 28 , wherein the process comprises at least two successive steps:
a step of applying to the keratin fibers a cosmetic composition comprising (b) at least one cationic (poly)methine fluorescent dye, followed by, a step of applying to the keratin fibers a cosmetic composition comprising (a) at least one or more anthraquinone dye of formula (I) and/or (II).
52 . The process according to claim 28 , wherein the process comprises at least two successive steps:
a step of applying to the fibers a cosmetic composition comprising (a) at least one anthraquinone dye of formula (I) and/or (II), followed by a step of applying to the keratin fibers a cosmetic composition comprising (b) at least one cationic (poly)methine fluorescent dye.
53 . The process according to claim 28 , wherein the pH of the cosmetic composition is between 6 and 11 inclusive.
54 . A cosmetic composition comprising (a) at least one anthraquinone dye chosen from the compounds of formulae (I) and/or (II) below, optical isomers thereof, geometrical isomers thereof, tautomers thereof, solvates thereof, or mixtures thereof:
wherein in formula (I) and/or (II):
X a , which may be identical or different, represents a bond, a heteroatom or a group chosen from an oxygen or sulfur atom, N(R a ), CO, SO, SO 2 , or combinations thereof, with R a representing a hydrogen atom or a (C 1 -C 6 )alkyl group optionally substituted with one or more hydroxyl groups;
Y represents: i) a hydrogen atom; ii) an alkali metal; iii) an alkaline-earth metal; iv) an ammonium group: N + R a R b R g R d or a phosphonium group: P + R a R b R g R d with R a R b , R g and R d , which may be identical or different, representing a hydrogen atom or a (C 1 -C 4 )alkyl group; or v) a thiol-function protecting group; or vi) the group (III) below:
R 1 , R 2 , R 3 , R 4 , R′ 1 , R′ 2 , R′ 3 and R′ 4 , which may be identical or different, represent an atom or a group chosen from:
hydrogen;
halogen such as bromine and chlorine,
hydroxyl,
C 1 -C 4 alkoxy,
hydroxysulfonyl (—SO 3 H) or sulfonate (—SO 3 − , M + ), with M + representing a cationic counterion;
optionally substituted C 1 -C 6 alkyl,
—NR 5 R 6 in which R 5 and R 6 , which may be identical or different, represent an atom or radical chosen from: i) hydrogen, ii) (C 1 -C 4 )alkylcarbonyl, iii) arylsulfonyl such as phenylsulfonyl (—SO 2 Ph), iv) Het-ALK-C(O)— with Het representing a heterocycloalkyl group which is optionally substituted and ALK represents a (C 1 -C 6 )alkylene group optionally substituted with one or more hydroxyl or (di)(hydroxy)(C 1 -C 4 )(alkyl)amino groups; v) optionally substituted aryl, vi) optionally substituted aryl(C 1 -C 4 )alkyl, viii) optionally substituted C 1 -C 20 alkyl, optionally interrupted with one or more heteroatoms and/or with one or more groups comprising at least one heteroatom;
a group of formula (a) below:
—N(R 7 )—X 1 —W 1 (a)
wherein in formula (a):
R 7 represents a hydrogen or a C 1 -C 4 alkyl radical,
X 1 represents a divalent radical chosen from C 1 -C 20 alkylene optionally interrupted with one or more heteroatoms or groups chosen from oxygen, nitrogen, sulfur, CO, SO, SO 2 , arylene, or combinations thereof;
W 1 represents a cationic radical chosen from:
with R 8 , R 9 , R 10 and R 11 , which may be identical or different, representing a C 1 -C 6 alkyl group, a benzyl radical, a C 1 -C 6 alkyl sulfonate radical; the radicals R 8 and R 9 optionally form, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising another non-nitrogen heteroatom;
n is an integer ranging from 1 to 3;
T 1 represents a linear or branched divalent hydrocarbon-based chain comprising from 1 to 20 carbon atoms, optionally interrupted with one or more heteroatoms or groups, or combinations thereof, chosen from oxygen, sulfur, N(R b ), C(O), —N + (R 8 )(R 9 )-An, optionally cationic and optionally substituted heteroaryl, An with R 8 and R 9 , which may be identical or different, represent a C 1 -C 6 alkyl radical; R b representing a hydrogen atom or a (hydroxy)(C 1 -C 4 )alkyl group;
being the part of the bond that is connected to the rest of the molecule; and
(b) at least one cationic (poly)methine fluorescent dye.Join the waitlist — get patent alerts
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